Modacrylic fibers containing compounds of the azulene series

ABSTRACT

A modacrylic textile fiber having uniformly dispersed therein, based on the weight of the fiber, from about 0.001 to about 0.01 weight percent of an acetone-soluble whitening agent of the azulene series.

United States Patent Otis Feb. 22, 1972 [54] MODACRYLIC FIBERS CONTAINING 2,823,239 2/ 1958 Lang et al. ..260/666 A COMPOUNDS OF THE AZULENE 2,838,580 6/1958 Ruzicka et al.. ..260/666 A SERIES 3,002,956 10/1961 Perri ...260/85.5 A X 3,155,737 11/1964 Hafner ..260/666 A [72] Inventor: Marshall V..0tis, Kingsport, Tenn. 3,254,046 5/1966 Mazzolini et al. ..260/4l C 3,288,888 1 1/1966 Wieckowski ...260/85.5 A X 1 Ass1gne= m Kodak Company, Rochester, 3,388,189 6/1968 Mazzolini et al ..260/85.5 A x 2 Filed: July 13 1976 Primary Examiner-Morris Liebman Assistant Examiner-Samuel L. Fox PP 54,600 Attorney-Charles R. Martin and Cecil D. Quillen, Jr.

[52] US. Cl. ..260/4l, 8/1 W, 264/211 51 Int. Cl. ..D06p 3/70, C08f45/l4 [571 ABSTRACT Field of Search ....260/41, 85.5 A modacrylic textile fiber having uniformly dispersed therein, 211 based on the weight of the fiber, from about 0.001 to about 0.0l weight percent of an acetone-soluble whitening agent of [56] References Cited the azulene series.

UNITED STATES PATENTS 13 Claims, N0 Drawings 2,766,304 10/ l956 Ziegler et al. ..260/ 666 A MODACRYLIC FIBERS CONTAINING COMPOUNDS OF THE AZULENE SERIES This invention relates to a modacrylic textile fiber having uniformly dispersed therein an acetone-soluble whitening agent of the azulene series. In another aspect this invention relates to a process for producing modacrylic fibers of improved whiteness by spinning the fibers from a solution containing acetone and an acetone-soluble whitening agent of the azulene series.

Modacrylic fibers have become a significant commercial fiber in recent years. Presently modacrylic fibers enjoy popularity for a variety of uses such as carpets, drapes, wigs, and the like.

Although modacrylic fibers are desirable for many applications, a significant problem exists in that the fibers tend to yellow after heat setting. This invention provides a valuable contribution to the art in that according to this invention a modacrylic fiber of improved whiteness can be produced.

In summary, one embodiment of this invention relates to a modacrylic textile fiber of improved whiteness having an acetone-soluble whitening agent of the azulene series uniformly dispersed throughout the fiber. In summary, another embodiment of this invention relates to a process for producing a modacrylic fiber of improved whiteness comprising the steps of l) preparing a spinning dope solution containing a fiber-forming modacrylic polymer, acetone and an acetone-soluble whitening agent of the azulene series, (2) spinning a fiber from the spinning dope and (3) heat setting the spun fiber.

Accordingly, an object of this invention is to provide a modacrylic textile fiber of improved whiteness.

Another object of this invention is to provide a process for producing a modacrylic textile fiber of improved whiteness.

Other objects, advantages, andfeatures of this invention will be readily apparent to those skilled in the art from the following description and appended claims.

The whitening agents of this invention are compounds of the azulene series and correspond to the general formula wherein R is hydrogen or an alkyl, aryl, alkaryltaralkyl or alkoxy radical. I

In one embodiment R can be an alkyl radical containing from one to 20 carbon atoms.

As is well known by those skilled in the art, when R is hydrogen in the above formula, the compound is often called azulene. When the carbon atoms contain substituents such as alkyl, the compounds are often named as an azulene derivative. For example, when methyl radicals are attached to carbon atoms number I and 4 and an isopropyl radical is attached to carbon atom number 7, the resulting compound can be named 1,4-dimethyl-7 -isopropyl azulene. Thus according to this invention the term azulene series means the compounds corresponding to the above general formula. Other suitable members of the azulene series include 2-isopropyl-4,8- dimethylazylene, 2-isopropyl-5-methylazulene, 1,3,5- trimethylazulene 1,3,5-trimethoxyazulene, 2-ethyl-8-methoxy-4-methylazulene, 2-ethyl-4-methylazulene, 2-phenylazu- 5- lene, 2-(octylphenyl)-azulene, S-benzylazulene, isopropylazulene, Z-ethylazulene, 2-laurylazulene, 5-octadecylazulene, 6-naphthylazulene.

The azulene series compounds useful in this invention, as well as methods for their preparation, are well known in the art and are described in U.S. Pat. No. 2,971,034 and the article entitled, The Azulenes, by Maxwell Gordon, Chemical Reviews, Vol. 50, pp. 127-200 1952).

According to this invention, any of the above-described compounds that act as whitening agents in modacrylic fibers can be used. Thus in this application the term whitening agent means any compound corresponding to the above general formula that when dispersed throughoutthe fiber will produce a modacrylic fiber whiter than a corresponding modacrylic fiber that has had the whitening agent omitted.

According to this invention, the whitening agent is uniformly dispersed throughout the fiber. Although the whitening agent can be placed in the fiber in any manner that will produce the fiber of this invention, in one embodiment the whitening agent is dissolved in the spinning dope solution and a fiber spun from the dope. The spinning dope can contain materials other than the solvent such as lubricants, dye promoters, viscosity modifiers and the like.

According to this invention, the whitening agent is acetone soluble and thus dissolves in a spinning dope containing acetone.

According to this invention, the whitening agent can, based on the weight of the fiber, comprise from about 0.00l to about 0.01 weight percent of the fiber and inanother embodiment can comprise from about 0.003 to about 0.008 weight percent of the fiber.

The modacrylic fibers useful in this invention can comprise any modacrylic fiber suitable for use in the invention. In one embodiment, the polymer which forms the modacrylic fiber can be comprised of, based on the weight of the polymer, from about 30 to about 70 weight percent acrylonitrile and from about 70 to about 30 weight percent vinyl chloride or vinylidene chloride. In another embodiment of the invention the fiber-forming polymer can comprise, based on the weight of the polymer, from 35 to 60 weight percent acrylonitrile and from 65 to 40 weight percent vinyl chloride or vinylidene chloride.

According to this invention the fiber-forming polymer can contain other polymers. Specifically, the acrylonitrile/vinyl chloride or vinylidene chloride polymer can be admixed with other dissimilar polymers such as polymers of acrylamides, methacrylamides, fumaramides, citraconamides, vinyl pyridines, styrene, itaconamides, maleamates, fumaramates, itaconamates, citraconamates, vinyl esters, substituted 'sytrenes, polymerizable unsaturated acids, vinylic ketones,

vinylic ethers, and similar well-known polymerizable monomers containing a single ethylenic unsaturation. Thus, for example, typical monomers which are suitably employed to form these polymers include acrylamide, N-methyl methacrylamide, N-isopropyl acrylamide, vinyl acetate, styrene, butyl acrylate, methyl acrylate, methyl methacrylate, N-methyl fumaramide, N-methyl maleamate, N-methyl citraconamate, a-methylstyrene, methyl vinyl ketone, ethyl vinyl ketone, isopropenyl acetate, 2-methyl-5-vinyl pyridine, 2-vinyl pyridine, ethylene, acrylic acid, and methacrylic acid. In this embodiment, based on the weight of the fiber forming polymer, the amount of acrylonitrile/vinyl chloride or vinylidene chloride polymer can vary from about 95 to about weight percent, and the amount of the dissimilar polymer can vary from about 5 to about 20 weight percent. Other materials such as stabilizers, inhibitors, catalysts, activators, and surfactants can be added to the polymer.

In this invention the fiber can contain materials other than the fiber-forming polymer such as stabilizers, dye promoters, lubricants, optical brighteners and the like.

The fibers of this invention are spun from a spinning dope solution and heatset according to methods well known in the art.

The following examples are presented to further illustrate the invention and are not to be interpreted as limiting the invention.

EXAMPLE 1 Several runs are made to illustrate the practice of the invention wherein the whitening agent is azulene. In these runs various quantities of azulene are uniformly dispersed in a l6-denier/filament modacrylic fiber useful in this invention. In these runs the fiber was spun from an acetone containing spinning dope and heat set according to methods well known in the art. Specifically, in a first run, based on the weight of the fiber, about 0.001 weight percent azulene is used, and in a second run about 0.005 weight percent azulene is used and in a third run about 0.01 weight percent azulene is used. After heat setting, fibers from all three runs are whiter than fibers of the same modacrylic composition but without the whitening agents of this invention.

This example demonstrates that the whitening agents of the invention, when used in quantities from about 0.001 to about 0.01 weight percent, result in a modacrylic fiber whiter than a corresponding modacrylic fiber that does not contain the whitening agents of this invention.

EXAMPLE 2 Several more runs are made to illustrate the practice of the invention when the whitening agent is 1,4-dimethyl-7- isopropylazulene. In a first run l6-denier/filament fibers were spun containing, based on the weight of the fiber, about 0.005 weight percent l,4-dimethul-7-isopropylazulene and in a second run the amount of l,4-dimethyl-7-isopropylazulene in the fiber was 0.01 weight percent. Heat set fibers from both runs are whiter than fibers of the same modacrylic fiber without the whitening agents of this invention.

This example demonstrates that whitening agents of the azulene series other than azulene can be used in the practice ofthis invention.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope ofthe invention.

lclaim:

l. A textile fiber comprising A. a fiber-forming polymer comprised of, based on the weight of the polymer,

1. about 30 to about 70 weight percent acrylonitrile and 2. about 70 to about 30 weight percent vinyl chloride or vinylidene chloride and B. uniformly dispersed throughout the fiber from about 0.001 to about 0.01 weight percent, based on the weight of the fiber, of an acetone-soluble whitening agent of the formula wherein R is hydrogen or an alkyl radical or an aryl radical and at least five of the R's are hydrogen. 2. The fiber of claim 1 wherein R is hydrogen.

3. The fiber of claim 1 wherein R attached to carbon atom number 1 is methyl,

R attached to carbon atom number 4 is methyl, and

R attached to carbon atom number 7 is isopropyl.

4. The fiber of claim 1 wherein the fiber-forming polymer comprises from 35 to 60 weight percent acrylonitrile and from 65 to 40 weight percent vinyl chloride or vinylidene chloride.

5. The fiber of claim 1 wherein the fiber-forming polymer comprises, based on the weight of the polymer, an admixture of from about 95 to about weight percent of a polymer of acrylonitrile and vinylidene chloride and from about 5 to about 20 weight percent ofa dissimilar polymer.

6. The fiber of claim 1 wherein the whitening agent is in the range of 0.003 to 0.008 weight percent.

7. A process comprising A. preparing a spinning dope solution comprising acetone and a fiber-forming olymer of, 1. based on the weig t ofthe polymer,

a. about 30 to about 70 weight percent acrylonitrile and b. about 70 to about 30 weight percent vinyl chloride or vinylidene chloride and 2. uniformly dispersed throughout the spinning dope an acetone soluble whitening agent of the formula R-O2 (IJ 6CR wherein R is hydrogen or an alkyfradical or an aryl radical and at least five of the Rs are hydrogen,

B. spinning a fiber from the spinning dope solution, and

C. heat setting the spun fiber.

8. The process of claim 7 wherein R is hydrogen,

9. The process of claim 7 wherein R attached to carbon atom number 1 is methyl,

R attached to carbon atom number 4 is methyl, and

R attached to carbon atom number 7 is isopropyl.

10. The process of claim 7 wherein the fiber-forming polymer comprises from 35 to 60 weight percent acrylonitrile and from 65 to 40 weight percent vinyl chloride or vinylidene chloride.

11. The process of claim 2 wherein the fiber-forming polymer comprises, based on the weight of the polymer, an admixture of from about to about 80 weight percent of a polymer of acrylonitrile and vinylidene chloride and from about 5 to about 20 weight percent ofa dissimilar polymer.

12. The process of claim 7 wherein the whitening agent is in the range of about 0.001 to about 0.0] weight percent, based on the weight of the fiber.

13. The process of claim 7 wherein the whitening agent is in the range of 0.003 to 0.008 weight percent, based on the weight ofthe fiber.

P(%-/%%F;O UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 5,644,272 I Dated February 22, 1972 Patent No.

InVntor(s) Marshall V. Otis It is Certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Claim 11, line 1, "2" should be ---7---,

Signed and sealed this 5th day of September 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attestlng Officer Commissioner of Patents TEC 1026! 

2. about 70 to about 30 weight percent vinyl chloride or vinylidene chloride and B. uniformly dispersed throughout the fiber from about 0.001 to about 0.01 weight percent, based on the weight of the fiber, of an acetone-soluble whitening agent of the formula
 2. The fiber of claim 1 wherein R is hydrogen.
 2. uniformly dispersed throughout the spinning dope an acetone soluble whitening agent of the formula
 3. The fiber of claim 1 wherein R attached to carbon atom number 1 is methyl, R attached to carbon atom number 4 is methyl, and R attached to carbon atom number 7 is isopropyl.
 4. The fiber of claim 1 wherein the fiber-forming polymer comprises from 35 to 60 weight percent acrylonitrile and from 65 to 40 weight percent vinyl chloride or vinylidene chloride.
 5. The fiber of claim 1 wherein the fiber-forming polymer comprises, based on the weight of the polymer, an admixture of from about 95 to about 80 weight percent of a polymer of acrylonitrile and vinylidene chloride and from about 5 to about 20 weight percent of a dissimilar polymer.
 6. The fibEr of claim 1 wherein the whitening agent is in the range of 0.003 to 0.008 weight percent.
 7. A process comprising A. preparing a spinning dope solution comprising acetone and a fiber-forming polymer of,
 8. The process of claim 7 wherein R is hydrogen.
 9. The process of claim 7 wherein R attached to carbon atom number 1 is methyl, R attached to carbon atom number 4 is methyl, and R attached to carbon atom number 7 is isopropyl.
 10. The process of claim 7 wherein the fiber-forming polymer comprises from 35 to 60 weight percent acrylonitrile and from 65 to 40 weight percent vinyl chloride or vinylidene chloride.
 11. The process of claim 2 wherein the fiber-forming polymer comprises, based on the weight of the polymer, an admixture of from about 95 to about 80 weight percent of a polymer of acrylonitrile and vinylidene chloride and from about 5 to about 20 weight percent of a dissimilar polymer.
 12. The process of claim 7 wherein the whitening agent is in the range of about 0.001 to about 0.01 weight percent, based on the weight of the fiber.
 13. The process of claim 7 wherein the whitening agent is in the range of 0.003 to 0.008 weight percent, based on the weight of the fiber. 